Polyolefin solution polymerization process and polymer

ABSTRACT

A catalyst composition comprising a zirconium complex of a polyvalent aryloxyether and a polymerization processes employing the same, especially a continuous, solution polymerization of ethylene and one or more C 3-30  olefins or diolefins to prepare interpolymers having improved processing properties, are disclosed.

CROSS REFERENCE STATEMENT

This application claims the benefit of U.S. Provisional Application60/801,182, filed May 17, 2006.

BACKGROUND OF THE INVENTION

Catalyst compositions based on well defined donor ligand containingmetal complexes, referred to as post-metallocene complexes have beenshown to give products having better comonomer incorporation and narrowmolecular weight distribution. However, these catalysts often have poorhigh temperature stability and suffer from poor catalytic efficiencies,especially at elevated polymerization temperatures.

Examples of one type of the foregoing post metallocene catalysts aredisclosed in U.S. Pat. No. 6,827,976, where Group 3-6 or Lanthanidemetal complexes, preferably Group 4 metal complexes, of bridged divalentaromatic ligands containing a divalent Lewis base chelating group aredisclosed.

Higher solution reaction temperatures are particularly desired forolefin polymerizations in order to improve operating efficiency and toproduce long chain branching in the resulting polymer. Long chainbranching in olefin polymers is believed to result in one embodimentfrom the incorporation of vinyl terminated polymers, generated in situby β-hydride elimination that results in vinyl group formation ingrowing polymer chains. These processes are benefited by use of highreaction temperatures and high monomer conversion conditions.Accordingly, selection of catalyst compositions capable of incorporatinglong chain branching, such as for example reincorporation of in situproduced vinyl terminated polymer, under the foregoing extreme reactionconditions is highly desired.

We have now discovered that certain metal complexes may be employed in asolution polymerization process to prepare high molecular weightethylene containing interpolymers containing relatively large quantitiesof long chain branching therein at high olefin conversions if certainprocess conditions are observed. The resulting polymer products possessdesirable properties such as better flexibility, reduced density(greater comonomer incorporation) and improved processability (lessenergy required for extrusion, reduced melt fracture and reduction ofsurface imperfections or “sharkskin” formation). In addition, we havediscovered that these catalyst compositions retain their high catalystactivity and long chain branch forming ability using relatively lowmolar ratios of conventional alumoxane cocatalysts. The use of reducedquantities of alumoxane cocatalysts (reduced by up to 90 percent ormore, compared to the quantities employed in conventional processes)allows for the preparation of polymer products having reduced metalcontent and consequently increased clarity, improved dielectricproperties and other enhanced physical properties. In addition, the useof reduced quantities of alumoxane cocatalysts results in reduction inpolymer production costs.

SUMMARY OF THE INVENTION

According to the present invention there is now provided a process forpolymerization of ethylene and one or more C₃₋₂₀ α-olefins undersolution polymerization conditions with a catalyst compositioncomprising a zirconium complex of a polyvalent aryloxyether whichaffords interpolymers having narrow molecular weight distribution andimproved processability.

Additionally, according to the invention it is possible to produceinterpolymers possessing relatively high molecular weights (withcorrespondingly low melt indices) and high levels of comonomerincorporation (low densities), having relatively high I₁₀/I₂, due to thepresence of long chain branching. This unique combination of polymerproperties is also attainable by use of low molar ratios (200 or less,preferably 100 or less, more preferably 80 or less, based on zirconium)of an alkylalumoxane cocatalyst or a trialkylaluminum-modified alumoxanecocatalyst. The polymers can be prepared under high temperature, highconversion conditions at high catalyst efficiencies.

The present invention is particularly advantageous for use undercontinuous solution polymerization conditions wherein a reaction mixturecomprising a metal complex, an activating cocatalyst or cocatalystmixture, optionally a chain transfer agent, and at least one C₂₋₂₀α-olefin is continuously added to a reactor operating under solutionpolymerization conditions, and polymer product is continuously orsemi-continuously removed therefrom. In one embodiment, the invention isused to prepare copolymers of ethylene and at least one C₃₋₂₀ α-olefin,preferably ethylene and at least one C₃₋₈ α-olefin, having improvedprocessability.

The invention is particularly suitable for production of resins that areused in the insulation layer of electrical wires and cables,particularly in medium and high voltage applications, films and extrudedobjects having improved surface appearance and reduced energyconsumption in their preparation.

DETAILED DESCRIPTION OF THE INVENTION

All references to the Periodic Table of the Elements herein shall referto the Periodic Table of the Elements, published and copyrighted by CRCPress, Inc., 2003. Also, any references to a Group or Groups shall be tothe Group or Groups reflected in this Periodic Table of the Elementsusing the IUPAC system for numbering groups. Unless stated to thecontrary, implicit from the context, or customary in the art, all partsand percents are based on weight and all test methods are current as ofthe filing date hereof. For purposes of United States patent practice,the contents of any patent, patent application, or publicationreferenced herein are hereby incorporated by reference in their entirety(or the equivalent US version thereof is so incorporated by reference)especially with respect to the disclosure of synthetic techniques,definitions (to the extent not inconsistent with any definitionsprovided herein) and general knowledge in the art.

The term “comprising” and derivatives thereof is not intended to excludethe presence of any additional component, step or procedure, whether ornot the same is disclosed herein. In order to avoid any doubt, allcompositions claimed herein through use of the term “comprising” mayinclude any additional additive, adjuvant, or compound whether polymericor otherwise, unless stated to the contrary. In contrast, the term,“consisting essentially of” excludes from the scope of any succeedingrecitation any other component, step or procedure, excepting those thatare not essential to operability. The term “consisting of” excludes anycomponent, step or procedure not specifically delineated or listed. Theterm “or”, unless stated otherwise, refers to the listed membersindividually as well as in any combination.

As used herein with respect to a chemical compound, unless specificallyindicated otherwise, the singular includes all isomeric forms and viceversa (for example, “hexane”, includes all isomers of hexaneindividually or collectively). The terms “compound” and “complex” areused interchangeably herein to refer to organic-, inorganic- andorganometal compounds. The term, “atom” refers to the smallestconstituent of an element regardless of ionic state, that is, whether ornot the same bears a charge or partial charge or is bonded to anotheratom. The term “heteroatom” refers to an atom other than carbon orhydrogen. Preferred heteroatoms include: F, Cl, Br, N, O, P, B, S, Si,Sb, Al, Sn, As, Se and Ge. The term “amorphous” refers to a polymerlacking a crystalline melting point as determined by differentialscanning calorimetry (DSC) or equivalent technique.

The term, “hydrocarbyl” refers to univalent substituents containing onlyhydrogen and carbon atoms, including branched or unbranched, saturatedor unsaturated, cyclic, polycyclic or noncyclic species. Examplesinclude alkyl-, cycloalkyl-, alkenyl-, alkadienyl-, cycloalkenyl-,cycloalkadienyl-, aryl-, and alkynyl-groups. “Substituted hydrocarbyl”refers to a hydrocarbyl group that is substituted with one or morenonhydrocarbyl substituent groups. The terms, “heteroatom containinghydrocarbyl” or “heterohydrocarbyl” refer to univalent groups in whichat least one atom other than hydrogen or carbon is present along withone or more carbon atom and one or more hydrogen atoms. The term“heterocarbyl” refers to groups containing one or more carbon atoms andone or more heteroatoms, but no hydrogen atoms. The bond between thecarbon atom and any heteroatom as well as the bonds between any twoheteroatoms, may be a single or multiple covalent bond or a coordinatingor other donative bond. Thus, an alkyl group substituted with aheterocycloalkyl-, aryl-substituted heterocycloalkyl-, heteroaryl-,alkyl-substituted heteroaryl-, alkoxy-, aryloxy-, dihydrocarbylboryl-,dihydrocarbylphosphino-, dihydrocarbylamino-, trihydrocarbylsilyl-,hydrocarbylthio-, or hydrocarbylseleno-group is within the scope of theterm heteroalkyl. Examples of specific heteroalkyl groups includecyanomethyl-, benzoylmethyl-, (2-pyridyl)methyl-, andtrifluoromethyl-groups.

As used herein the term “aromatic” refers to a polyatomic, cyclic,conjugated ring system containing (4δ+2) π-electrons, wherein δ is aninteger greater than or equal to 1. The term “fused” as used herein withrespect to a ring system containing two or more polyatomic, cyclic ringsmeans that with respect to at least two rings thereof, at least one pairof adjacent atoms is included in both rings. The term “aryl” refers to amonovalent aromatic substituent which may be a single aromatic ring ormultiple aromatic rings which are fused together, linked covalently, orlinked to a common group such as a methylene or ethylene moiety.Examples of aromatic ring(s) include phenyl, naphthyl, anthracenyl, andbiphenyl, among others.

“Substituted aryl” refers to an aryl group in which one or more hydrogenatoms bound to any carbon is replaced by one or more functional groupssuch as alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heterocycloalkyl, substituted heterocycloalkyl, halogen, alkylhalos (forexample, CF₃), hydroxy, amino, phosphido, alkoxy, amino, thio, nitro,and both saturated and unsaturated cyclic hydrocarbons which are fusedto the aromatic ring(s), linked covalently or linked to a common groupsuch as a methylene or ethylene moiety. The common linking group mayalso be a carbonyl as in benzophenone, or oxygen as in diphenylether, ornitrogen as in diphenylamine.

Embodiments of the invention provide a new solution process for makingolefin polymers using a catalyst composition comprising a transitionmetal complex at high temperature, high catalyst efficiency and highmonomer conversion, wherein the produced polymers comprise increasedlong chain branching content. Highly desirably, the produced polymersare of high molecular weight (I₂<5.0) and possess I₁₀/I₂≧10 with anarrow molecular weight distribution (Mw/Mn<3.0), thereby indicating thepresence of long chain branching. Such polymers are suitably employedwhere improved extrusion performance is desired, such as in molding andextrusion grades of polymer especially for film, foam or wire and cableinsulating applications.

The term “polymer” as used herein refers to a macromolecular compoundprepared by polymerizing one or more monomers. A polymer refers tohomopolymers, copolymers, terpolymers, interpolymers, and so on. Theterm “interpolymer” is used herein interchangeably with the termcopolymer to refer to polymers incorporating in polymerized form atleast two copolymerizable monomers, or incorporating long chainbranching as a result of chain termination/olefin formation reactions insitu, and reincorporation of the in situ formed olefin. Accordingly,copolymers may result from the polymerization of a single monomer, underthe correct operating conditions. The least prevalent monomer in theresulting copolymer or interpolymer is generally referred to by the term“comonomer”. The chain length of the resulting long chain branchesreferred to above, is consequently longer than the carbon lengthresulting from polymerization of any deliberately added comonomer, andin particular, is longer than 6 carbons for ethylene/1-octenecopolymers. The presence of long chain branching may also be detected bythe increased shear sensitivity of the polymer, as disclosed inEP-A-608,369, and elsewhere, or determined by Melt Index Ratio (MIR), aratio of polymer melt viscosities measured under differing loads,especially I₂₁/I₂.

The process described herein may be employed to prepare any olefininterpolymer, especially copolymers of ethylene with one or more C₃₋₂₀olefins, and optionally one or more C₄₋₂₀ diolefins, and, especially,ethylene/propylene, ethylene/1-butene, ethylene/1-hexene,ethylene/4-methyl-1-pentene, ethylene/styrene,ethylene/propylene/styrene, and ethylene/1-octene copolymers, as well ascopolymers of ethylene, propylene and a non-conjugated diene, forexample, EPDM interpolymers.

Polymerization conditions generally refer to temperature, pressure,monomer content (including comonomer concentration), catalystconcentration, cocatalyst concentration, monomer conversion, or otherconditions that influence the properties of the resulting polymer. Byoperation according to the prescribed polymerization conditions of theinvention high molecular weight polymers may be prepared havingrelatively high comonomer incorporation with high catalyst activities,low cocatalyst usage and high I₁₀/I₂ or MIR. In particular, activities(based on weight of polymer to weight of transition metal) greater than0.5 g/μg, preferably greater than 0.55 g/μg, and even greater than 0.6g/μg are possible.

Polymer weight-average molecular weight (M_(w)) is measured by gelpermeation chromatography, one technique of which as described in U.S.Pat. No. 5,272,236. Alternatively, melt index, I₂, I₁₀ or I₂₁, measured,for example, according to ASTM D-1238 may be employed as an indicationof molecular weight. Generally, melt index is inversely related to themolecular weight of the polymer. The higher the molecular weight, thelower the melt index, although the relationship is not necessarilylinear.

One embodiment of this invention entails a process and the resultingpolymer product which process comprises contacting ethylene and one ormore C₃₋₂₀ α-olefins in a solution polymerization process. The presentinvented process is particularly advantageous for use underpolymerization conditions wherein a reaction mixture comprising metalcomplex, activating cocatalyst, ethylene, and at least one C₃₋₂₀α-olefin comonomer (or the individual components thereof) iscontinuously or intermittently added to a reactor operating undersolution polymerization conditions, optionally in the additionalpresence of a chain transfer agent, and polymerized product iscontinuously or semi-continuously removed therefrom. This process canconsist of:

1) Polymerizing ethylene and one or more C₃₋₂₀ α-olefins and ordiolefins using a zirconium complex and a cocatalyst, under continuous,solution polymerization onditions at a temperature from 120 to 250° C.,preferably from 130 to 250° C., under high ethylene conversionconditions (>85 percent, preferably >90 percent) which results in apolymer with a density between 0.855 and 0.950 g/cm³, preferably between0.855 and 0.885 g/cm³, and a low melt index (I₂<2.0) with a catalystefficiency of greater than 0.5 g_(polymer)/μg_(metal), and I₁₀/I₂≧10 orMIR from 30 to 80.

2) Polymerizing ethylene and one or more C₃₋₂₀ α-olefins and ordiolefins using a zirconium complex and from 10 to 200 moles per molezirconium of an alumoxane, under continuous, solution polymerizationconditions at a temperature from 120 to 250° C., preferably from 130 to250° C., under high ethylene conversion conditions (>85 percent,preferably >90 percent) which results in a polymer with a densitybetween 0.855 and 0.950 g/cm³, preferably between 0.855 and 0.885 g/cm³,and I₂<5.0 with a catalyst efficiency of greater than 0.5g_(polymer)/μg_(metal), and low catalyst and cocatalyst residuesproducing a polymer having a dissipation factor at 130° C. of less than1 percent, preferably less than 0.5 percent and even more preferablyless than 0.25 percent and I₁₀/I₂≧10 or MIR from 30 to 80.

3) Polymerizing ethylene and one or more C₃₋₈ α-olefins using azirconium complex and an activating cocatalyst under continuous,solution polymerization conditions at a temperature from 120 to 250° C.,preferably from 130 to 250° C., under high ethylene conversionconditions (>85 percent, preferably >90 percent) which results in apolymer with a density between 0.855 and 0.950 g/cm³, preferably between0.855 and 0.885 g/cm³, a melt index (MI) from 0.1 to 40, andI₁₀/I₂>11.75 (MI)^(−0.188), preferably I₁₀/I₂>12.72 (MI)^(−0.168).

Surprisingly, the present metal complexes are capable of producingpolymers of extremely high molecular weight under a variety ofpolymerization conditions, and catalyst efficiencies of greater than 0.5g_(polymer)/μg_(metal) thereby allowing the use of a chain transferagent to control molecular weight without sacrificing molecular weightdistribution or long chain branching content. A sufficient quantity ofchain transfer agent is preferably used so that a substantial decreasein molecular weight (>10 percent) occurs compared to a comparativepolymerization without the use of chain transfer agent. When the chaintransfer agent is hydrogen, at least 0.01 mol percent (based onethylene) is used, and a maximum of about 2 mol percent is used.Especially surprising is the fact that very low density (high comonomercontent) polymers can be prepared with high levels of chain transferagents, while still affording polymers with high I₁₀/I₂, optionallyusing low levels of alumoxane activators. Generally, use of high levelsof chain transfer agent and high levels of comonomer with conventionalcatalysts results in production of increased levels of non-polymerizableend-groups, thereby resulting in a reduction of long chain branchformation and production of polymers having lower I₁₀/I₂.

The metal complexes are activated in various ways to yield catalystcompounds having a vacant coordination site that will coordinate,insert, and polymerize addition polymerizable monomers, especiallyolefin(s). For the purposes of this patent specification and appendedclaims, the term “activator” or “cocatalyst” is defined to be anycompound or component or method which can activate the metal complex inthe foregoing manner. Non-limiting examples of suitable activatorsinclude Lewis acids, non-coordinating ionic activators, ionizingactivators, organometal compounds, and combinations of the foregoingsubstances capable of converting the neutral metal complex to acatalytically active species.

It is believed, without desiring to be bound by such belief, that in oneembodiment of the invention, catalyst activation may involve formationof a cationic, partially cationic, or zwitterionic species, by means ofproton transfer, oxidation, or other suitable activation process. It isto be understood that the present invention is operable and fullyenabled regardless of whether or not such an identifiable cationic,partially cationic, or zwitterionic species actually results during theactivation process, also interchangeably referred to herein as an“ionization” process or “ionic activation process”.

Ionizing cocatalysts may contain an active proton, or some other cationassociated with, but not coordinated to or only loosely coordinated to,an anion of the ionizing compound. Such compounds are described inEuropean publications EP-A-570982, EP-A-520732, EP-A-495375,EP-A-500944, EP-A-277 003 and EP-A-277004, and U.S. Pat. Nos. 5,153,157,5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124.Preferred among the foregoing activators are ammonium cation containingsalts, especially those containing trihydrocarbyl-substituted ammoniumcations containing one or two C₁₀₋₄₀ alkyl groups, especiallymethylbis(octadecyl)-ammonium- andmethylbis(tetradecyl)-ammonium-cations and a non-coordinating anion,especially a tetrakis(perfluoro)arylborate anion, especiallytetrakis(pentafluorophenyl)borate. It is further understood that thecation may comprise a mixture of hydrocarbyl groups of differinglengths. For example, the protonated ammonium cation derived from thecommercially available long-chain amine comprising a mixture of two C₁₄,C₁₆ or C₁₈ alkyl groups and one methyl group. Such amines are availablefrom Chemtura Corp., under the trade name Kemamine™ T9701, and fromAkzo-Nobel under the trade name Armeen™ M2HT. A most preferred ammoniumsalt activator is methyldi(C₁₄₋₂₀alkyl)ammoniumtetrakis(pentafluorophenyl)borate.

Activation methods using ionizing ionic compounds not containing anactive proton but capable of forming active catalyst compositions, suchas ferrocenium salts of the foregoing non-coordinating anions are alsocontemplated for use herein, and are described in EP-A-426637,EP-A-573403 and U.S. Pat. No. 5,387,568. Also included is the use ofstrong Lewis acids, especially tris(perfluoro)aryl borane compounds,such as tris(pentafluorophenyl)borane, which are capable of abstractionof a ligand groups, especially a hydrocarbyl ligand, thereby forming anon-coordinating counter anion for the cationic derivative of the metalcomplex.

A class of cocatalysts comprising non-coordinating anions genericallyreferred to as expanded anions, further disclosed in U.S. Pat. No.6,395,671, may be suitably employed to activate the metal complexes ofthe present invention for olefin polymerization. Generally, thesecocatalysts (illustrated by those having imidazolide, substitutedimidazolide, imidazolinide, substituted imidazolinide, benzimidazolide,or substituted benzimidazolide anions) may be depicted as follows:

wherein:

A*⁺ is a cation, especially a proton containing cation, and preferablyis a trihydrocarbyl ammonium cation containing one or two C₁₀₋₄₀ alkylgroups, especially a methyldi(C₁₄₋₂₀alkyl)ammonium-cation,

R⁴, independently each occurrence, is hydrogen or a halo, hydrocarbyl,halocarbyl, halohydrocarbyl, silylhydrocarbyl, or silyl, (includingmono-, di- and tri(hydrocarbyl)silyl) group of up to 30 atoms notcounting hydrogen, preferably C₁₋₂₀ alkyl, and

J*′ is tris(pentafluorophenyl)borane or tris(pentafluorophenyl)alumane).

Examples of these catalyst activators includetrihydrocarbylammonium-salts, especially,methyldi(C₁₄₋₂₀alkyl)ammonium-salts of:bis(tris(pentafluorophenyl)borane)imidazolide,bis(tris(pentafluorophenyl)borane)-2-undecylimidazolide,bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolide,bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolide,bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolide,bis(tris(pentafluorophenyl)borane)imidazolinide,bis(tris(pentafluorophenyl)borane)-2-undecylimidazolinide,bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolinide,bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolinide,bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolinide,bis(tris(pentafluorophenyl)borane)-5,6-dimethylbenzimidazolide,bis(tris(pentafluorophenyl)borane)-5,6-bis(undecyl)benzimidazolide,bis(tris(pentafluorophenyl)alumane)imidazolide,bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolide,bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolide,bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolide,bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolide,bis(tris(pentafluorophenyl)alumane)imidazolinide,bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolinide,bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolinide,bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolinide,bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolinide,bis(tris(pentafluorophenyl)alumane)-5,6-dimethylbenzimidazolide, andbis(tris(pentafluorophenyl)alumane)-5,6-bis(undecyl)benzimidazolide.

Other activators include those described in PCT publication WO 98/07515such as tris(2,2′,2″-nonafluorobiphenyl)fluoroaluminate. Combinations ofactivators are also contemplated by the invention, for example,alumoxanes and ionizing activators in combinations, see for example,EP-A-0 573120, PCT publications WO 94/07928 and WO 95/14044 and U.S.Pat. Nos. 5,153,157 and 5,453,410. WO 98/09996 describes activatingcatalyst compounds with perchlorates, periodates and iodates, includingtheir hydrates. WO 99/18135 describes the use of organoboroaluminumactivators. EP-A-781299 describes using a silylium salt in combinationwith a non-coordinating compatible anion. Other activators or methodsfor activating a catalyst compound are described in for example, U.S.Pat. Nos. 5,849,852, 5,859,653, 5,869,723, EP-A-615981, and PCTpublication WO 98/32775.

Another suitable class of organometal activators or cocatalysts arealumoxanes, also referred to as alkylaluminoxanes. Alumoxanes are wellknown activators for use with metallocene type catalyst compounds toprepare addition polymerization catalysts. There are a variety ofmethods for preparing alumoxanes and modified alumoxanes, non-limitingexamples of which are described in U.S. Pat. Nos. 4,665,208, 4,952,540,5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924, 018, 4,908,463,4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157,137,5,103,031, 5,391,793, 5,391,529, 5,693,838, 5,731,253, 5,731,4515,744,656; European publications EP-A-561476, EP-A-279586 andEP-A-594218; and PCT publication WO 94/10180. Preferred alumoxanes areLewis acid modified alumoxanes, especially tri(C₃₋₆)alkylaluminummodified methylalumoxane, including tri(isobutyl)aluminum modifiedmethalumoxane, available commercially as MMAO-3A or tri(n-octyl)aluminummodified methalumoxane, available commercially as MMAO-12, from AkzoNobel, Inc.

It is within the scope of this invention to use alumoxane(s) or modifiedalumoxane(s) as an activator or as a tertiary component in the inventedprocess. That is, the compound may be used alone or in combination withother activators, either neutral or ionic, such as tri(alkyl)ammoniumtetrakis(pentafluorophenyl)borate compounds, trisperfluoroarylcompounds, polyhalogenated heteroborane anions as disclosed in WO98/43983, and combinations thereof. When used as a tertiary component,the amount of alumoxane employed is generally less than that necessaryto effectively activate the metal complex when employed alone. In thisembodiment, it is believed, without wishing to be bound by such belief,that the alumoxane does not contribute significantly to actual catalystactivation. Not withstanding the foregoing, it is to be understood thatsome participation of the alumoxane in the activation process is notnecessarily excluded.

Suitable alumoxanes include polymeric or oligomeric alumoxanes,especially methylalumoxane (MAO) as well as Lewis acid-modifiedalumoxanes, especially trihydrocarbylaluminum-, halogenatedtri(hydrocarbyl)aluminum- or halogenated tri(hydrocarbyl)boron-modifiedalumoxanes, having from 1 to 10 carbons in each hydrocarbyl orhalogenated hydrocarbyl group. Such activating cocatalysts arepreviously disclosed in U.S. Pat. Nos. 6,214,760, 6,160,146, 6,140,521,and 6,696,379, and elsewhere. Preferred Lewis acid-modified alumoxanecompounds are tri(i-butyl)aluminum-modified methalumoxane andtri(n-octyl)aluminum-modified methalumoxane containing from 10 to 30,preferably 15 to 25 mole percent i-butyl content and 10 to 20,preferably 12 to 18 mole percent n-octyl contents, respectively, saidmolar percents based on total alkyl ligand content. The alumoxane orLewis acid-modified alumoxane activator is preferably utilized in molarratios cocatalyst:catalyst from 20-200, more preferably from 20-150, andmost preferably from 20-80.

Because of the ability to be activated at relatively low levels ofalumoxane or Lewis acid modified alumoxane cocatalysts while maintaininghigh catalyst efficiency, the present zirconium complexes can achievereduced levels of cocatalyst byproducts in the resulting polymer alongwith long chain branch formation in the resulting polymer. This in turnallows the polymers to be employed in demanding applications that havebeen previously unsuited for ethylene/α-olefin interpolymers, such aswire and cable electrical insulation and extrusion forming process forprofiles, pipes, and other applications, while retaining goodflexibility and processing properties.

Multiple reactor polymerization processes are suitably employed in thepresent invention. Examples include such systems as are disclosed inU.S. Pat. No. 3,914,342, among others. The multiple reactors can beoperated in series or in parallel, with at least one catalystcomposition according to the present invention employed in at least oneof the reactors. One or both reactors may also contain at least twocatalysts which have different comonomer incorporation capability and/ordifferent molecular weight capability. In one embodiment, a relativelyhigh molecular weight product (M_(w) from 100,000 to over 1,000,000,more preferably 200,000 to 500,000) is formed while in the secondreactor a product of a relatively low molecular weight (M_(w) 2,000 to300,000) is formed. Both of these reactor products can have similar ordifferent densities. The final product is a mixture of the two reactoreffluents which are combined prior to devolatilization to result in auniform mixing of the two polymer products. In another embodiment, themolecular weight of the products from both reactors is nearly the samebut the densities vary to the extent that one of the reactors produces apolymer with density in the range of 0.865-0.895, while the otherreactor produces polymer with a different density in the range of0.885-0.950. Such a dual reactor/dual catalyst process allows for thepreparation of products with tailored properties. In one embodiment, thereactors are connected in series, that is, the effluent from the firstreactor is charged to the second reactor and fresh monomer, solvent andhydrogen is optionally added to the second reactor. Reactor conditionsare adjusted such that the weight ratio of polymer produced in the firstreactor to that produced in the second reactor is ideally in the rangefrom 20:80 to 80:20. It will be appreciated by the skilled artisan thatthe foregoing dual reactor process is capable of producing polymershaving broadened molecular weight distribution or polydispersity index(PDI). Preferred polymers made in the foregoing manner have PDI from 2.8to 10.0, more preferably from 3.0 to 7.0. In addition, in a desirableembodiment, the high molecular weight component contains higherquantities of comonomer (lower density) than the low molecular weightcomponent.

In one embodiment, one of the reactors in the polymerization process,including the first of two reactors operating in series, contains aheterogeneous Ziegler-Natta catalyst or a chromium containing catalyst,such as one of the numerous such catalysts known in the art. Examples ofZiegler-Natta catalysts include, but are not limited to, titanium-basedcatalysts supported on MgCl₂, and additionally comprise compounds ofaluminum containing at least one aluminum-alkyl bond. SuitableZiegler-Natta catalysts and their preparation include, but are notlimited to, those disclosed in U.S. Pat. Nos. 4,612,300, 4,330,646, and5,869,575. Suitable chromium based catalysts are those disclosed in U.S.Pat. Nos. 4,981,927, 4,835,219, 4,564,660, 4,173,548, 3,953,413, andelsewhere.

Single reactor, multiple catalyst processes are also useful in thepresent invention. In one embodiment, two or more catalysts areintroduced into a single reactor at the high monomer conversionconditions that are herein disclosed, wherein each catalyst inherentlyproduces different polyolefin copolymers. In one embodiment, arelatively high molecular weight product (M_(w) from 100,000 to over1,000,000, more preferably 200,000 to 500,000) is formed from onecatalyst while a product of a relatively low molecular weight (M_(w)2,000 to 300,000) is formed from the other catalyst. Both of thesecatalyst compositions can have similar or different comonomerincorporation ability, at least one of which comprises a metal complexas set forth herein. The resulting polymer will have propertiesdependent on the ratio of the two catalysts that are employed in thesingle reactor. Suitable combinations of polymer molecular weight,comonomer incorporation ability, processes, and ratios of catalysts forsuch products are disclosed in U.S. Pat. No. 6,924,342. Due to theunique compatibility of the present catalyst compositions with otherolefin polymerization catalysts, including Ziegler/Natta catalysts, thesecond catalyst composition may comprise a metal complex as hereindisclosed, a metallocene or other π-bonded ligand group containing metalcomplex (including constrained geometry metal complexes), or apolyvalent heteroatom ligand group containing metal complex, especiallypolyvalent pyridylamine or imidizolylamine based complexes andtetradendate oxygen-ligated biphenylphenol based Group 4 metalcomplexes.

Metal Complexes

Suitable metal complexes for use according to the present inventioninclude compounds corresponding to the formula:

where:

R²⁰ independently each occurrence is a arylene- or inertly substitutedarylene-group of from 6 to 20 atoms not counting hydrogen or any atomsof any substituent, said group being substituted at the positionadjacent to the oxyl-metal bond with a cyclic ligand, said cyclic ligandcontaining from 6 to 30 atoms not counting hydrogen;

T³ is a divalent hydrocarbon or silane group having from 1 to 20 atomsnot counting hydrogen, or an inertly substituted derivative thereof; and

R^(D) independently each occurrence is a monovalent ligand group of from1 to 20 atoms, not counting hydrogen, or two R^(D) groups together are adivalent ligand group of from 1 to 20 atoms, not counting hydrogen.

Preferably, such complexes correspond to the formula:

wherein:

Ar² independently each occurrence is phenylene or an alkyl-, aryl-,alkoxy- or amino-substituted phenylene group of from 6 to 20 atoms notcounting hydrogen or any atoms of any substituent, and furthersubstituted at the position adjacent to the oxyl-metal bond with apolycyclic aryl group containing from 6 to 30 atoms not countinghydrogen;

T³ is a divalent hydrocarbon bridging group of from 2 to 20 atoms notcounting hydrogen, preferably a divalent substituted or unsubstitutedC₃₋₆ aliphatic, cycloaliphatic, or bis(alkylene)-substitutedcycloaliphatic group; and

R^(D) independently each occurrence is a monovalent ligand group of from1 to 20 atoms, not counting hydrogen, or two R^(D) groups together are adivalent ligand group of from 1 to 40 atoms, not counting hydrogen.

More preferred examples of metal complexes suitable for use hereininclude compounds of the formula:

where

Ar⁴ independently each occurrence is C₆₋₂₀ aryl or inertly substitutedderivatives thereof, especially 3,5-di(isopropyl)phenyl,3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrole-1-yl, naphthyl,anthracen-5-yl, 1,2,3,4,6,7,8,9-octahydroanthracen-5-yl;

T⁴ independently each occurrence is a propylene-1,3-diyl group, acyclohexan-1,2-diyl group, a bis(alkylene)cyclohexan-1,2-diyl group, acyclohexen-4,5-diyl group, or an inertly substituted derivative thereof;

R²¹ independently each occurrence is hydrogen, halo, hydrocarbyl,trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino ofup to 50 atoms not counting hydrogen; and

R^(D), independently each occurrence is halo or a hydrocarbyl ortrihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2R^(D) groups together are a divalent hydrocarbylene, hydrocarbadiyl ortrihydrocarbylsilyl group of up to 40 atoms not counting hydrogen.

Especially preferred metal complexes are compounds of the formula:

where, Ar⁴, independently each occurrence, is dibenzo-1H-pyrrole-1-yl oranthracen-5-yl,

R²¹ independently each occurrence is hydrogen, halo, hydrocarbyl,trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino ofup to 50 atoms not counting hydrogen;

T⁴ is propan-1,3-diyl, cyclohexanediyl, cyclohexen-4,5-diyl, orbis(methylene)cyclohexan-1,2-diyl; and

R^(D), independently each occurrence is halo or a hydrocarbyl ortrihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2R^(D) groups together are a hydrocarbylene, hydrocarbadiyl orhydrocarbylsilanediyl group of up to 40 atoms not counting hydrogen.

Compared to metal complexes comprising a 1,4-butanediyl T⁴ group, theforegoing complexes demonstrate improved catalyst efficiencies,especially at elevated polymerization temperatures. Most highlypreferred metal complexes according to the invention correspond to theformulas:

wherein, R^(D) independently each occurrence is chloro, methyl orbenzyl.

Specific examples of suitable metal complexes are the followingcompounds:

-   A)    bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-1,3-cyclohexanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-1,3-cyclohexanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-1,3-cyclohexanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-1,3-cyclohexanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-1,3-cyclohexanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-1,3-cyclohexanediylzirconium (IV)    dibenzyl-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5-cyclohexenediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5-cyclohexenediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5-cyclohexenediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5-cyclohexenediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5-cyclohexenediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5-cyclohexenediylzirconium (IV)    dibenzyl-   B)    bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)-1,3-propanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)-1,3-propanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)-1,3-propanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)-1,3-propanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)-1,3-propanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)-1,3-propanediylzirconium (IV)    dibenzyl-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dibenzyl;-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)-trans    1,2-cyclohexanediylzirconium (IV) dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis    4,5-cyclohexenediylzirconium (IV) dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium (IV)    dibenzyl,-   C)    bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)-1,3-propanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)-1,3-propanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)-1,3-propanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)-1,3-propanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)-1,3-propanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)-1,3-propanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans-1,2-cyclohexanediyl    zirconium (IV) dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dibenzyl-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium (IV)    dibenzyl-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis    4,5-cyclohexenediylzirconium (IV) dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium (IV)    dichloride, and-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium (IV)    dibenzyl.

The foregoing metal complexes may be conveniently prepared by standardmetallation and ligand exchange procedures involving a source of thetransition metal and a neutral polyfunctional ligand source. Inaddition, the complexes may also be prepared by means of an amideelimination and hydrocarbylation process starting from the correspondingtransition metal tetraamide and a hydrocarbylating agent, such astrimethylaluminum. The techniques employed are the same as or analogousto those disclosed in U.S. Pat. Nos. 6,320,005, 6,103,657, WO 02/38628,WO 03/40195, US-A-2004/0220050, and elsewhere.

The metal complex is activated to form the active catalyst compositionby combination with the cocatalyst. The activation may occur prior toaddition of the catalyst composition to the reactor with or without thepresence of other components of the reaction mixture, or in situ throughseparate addition of the metal complex and activating cocatalyst to thereactor.

Monomers

Suitable olefin mixtures for use herein include mixtures of ethylenewith one or more C₃₋₃₀ aliphatic-, cycloaliphatic- or aromatic-compounds(comonomers) containing one or more ethylenic unsaturations. Examplesinclude aliphatic-, cycloaliphatic- and aromatic olefins or diolefins.Preferred comonomers include, but are not limited to, propylene,isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, and 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene,4-methyl-1-pentene, 4,6-dimethyl-1-heptene, vinylcyclohexane, styrene,cyclopentene, cyclohexene, cyclooctene, 1,3-butadiene, 1,3-pentadiene,1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene,4-vinylcyclohexene, dicyclopentadiene, norbornadiene,ethylidenenorbornene, and mixtures thereof.

The novel processes described herein are well suited for the productionof olefin polymers comprising monovinylidene aromatic monomers includingstyrene, o-methyl styrene, p-methyl styrene, t-butylstyrene, andmixtures thereof. In particular, interpolymers comprising ethylene andstyrene can be advantageously prepared by following the teachingsherein. Optionally, copolymers comprising ethylene, styrene and/or aC₃₋₂₀ alpha olefin, and further optionally comprising a conjugated ornon-conjugated C₄₋₂₀ diene can be prepared.

Suitable non-conjugated dienes include straight chain-, branched chain-or cyclic-hydrocarbon dienes having from 6 to 15 carbon atoms. Examplesof suitable non-conjugated dienes include, but are not limited to,straight chain acyclic dienes, such as 1,4-hexadiene, 1,6-octadiene,1,7-octadiene, 1,9-decadiene, branched chain acyclic dienes, such as5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene;3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyricene anddihydroocinene, single ring alicyclic dienes, such as1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and1,5-cyclododecadiene, and multi-ring alicyclic fused and bridged ringdienes, such as tetrahydroindene, methyl tetrahydroindene,dicyclopentadiene, bicyclo-(2,2,1)-hepta-2,5-diene; alkenyl, alkylidene,cycloalkenyl and cycloalkylidene norbornenes, such as5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene,5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene,5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, and norbornadiene.Of the dienes typically used to prepare EPDMs, the particularlypreferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene(ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene (MNB),and dicyclopentadiene (DCPD). The most especially preferred diene is5-ethylidene-2-norbornene (ENB).

In general, the polymerization may be accomplished at conditions wellknown in the prior art for olefin solution polymerization reactions.Preferred polymerization temperatures are dependent upon the comonomercontent of the resulting polymer. For polymers of densities ranging from0.855 to 0.885 g/cc, the preferred temperatures range from 120-250° C.,more preferably from 150-220° C. For polymers of densities ranging from0.885 to 0.955 g/cc, the preferred temperatures range from 160-250° C.,more preferably from 180-250° C. Preferred polymerization pressures arefrom atmospheric to 3000 atmospheres (100 kPa to 300 MPa), morepreferably from 1 MPa to 10 MPa. In most polymerization reactions themolar ratio of catalyst:polymerizable compound employed is from 10⁻¹²:1to 10⁻¹:1, more preferably from 10⁻¹¹:1 to 10⁻⁵:1. Highly desirably, thereaction is conducted under continuous, solution polymerizationconditions, that is, conditions wherein the monomer or monomers arecontinuously added to a reactor operating under solution polymerizationconditions, and polymerized product is continuously or semi-continuouslyremoved and recovered or forwarded to a second reactor.

Desirably, the polymerization mixture comprises an aliphatic oralicyclic liquid diluent. Examples of such aliphatic or alicyclic liquiddiluents include straight and branched-chain hydrocarbons such asisobutane, butane, pentane, hexane, heptane, octane, and mixturesthereof; alicyclic hydrocarbons such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof; andperfluorinated hydrocarbons such as perfluorinated C₄₋₁₀ alkanes, andthe like. Small quantities of aromatic hydrocarbons such as toluene,ethylbenzene or xylene may be included as well, but are not preferred.Mixtures of the foregoing are also suitable. A preferred liquid diluentis a hydrogenated oligomeric aliphatic hydrocarbon mixture having adistillation, ASTM D 86, IBP of 118° C., distillation, ASTM D 86, DryPoint of 137° C., and Specific Gravity, 15.6° C., ASTM D 1250 of 0.72sold commercially under the trade designation Isopar™ E, available fromExxonMobil Corporation.

The use of molecular weight control agents or chain transfer agents inthe present process is desired. Examples of such molecular weightcontrol agents include hydrogen, trialkyl aluminum compounds, or otherknown chain transfer agents. Hydrogen is a most preferred molecularweight control agent or chain transfer agent. A particular benefit ofthe use of the present invention is the ability (depending on reactionconditions) to produce narrow molecular weight distributionethylene/α-olefin interpolymers. Preferred polymers have Mw/Mn of lessthan 3.0, more preferably less than 2.6. Such narrow molecular weightdistribution polymer products are highly desirable due to improvedtensile strength properties as well as reduced levels of extractablesand metal values.

Without limiting in any way the scope of the invention, one means forcarrying out the present polymerization process is as follows. In astirred-tank reactor, the monomers to be polymerized are introducedcontinuously together with any solvent or diluent. The reactor containsa liquid phase composed substantially of monomers together with anysolvent or diluent and dissolved polymer. Catalyst along with cocatalystand optionally chain transfer agent are continuously or intermittentlyintroduced in the reactor liquid phase or any recycled portion thereof.The reactor temperature may be controlled by adjusting thesolvent/monomer ratio, the catalyst addition rate, as well as by use ofcooling or heating coils, jackets or both. The polymerization rate iscontrolled by the rate of catalyst addition. Pressure is controlled bythe monomer flow rate and partial pressures of volatile components. Theethylene content of the polymer product is determined by the ratio ofethylene to comonomer in the reactor, which is controlled bymanipulating the respective feed rates of these components to thereactor. The polymer product molecular weight is controlled, optionally,by controlling other polymerization variables such as the temperature,monomer concentration, or by the flow rate of the previously mentionedchain transfer agent. Upon exiting the reactor, the effluent iscontacted with a catalyst kill agent such as water, steam or an alcohol.The polymer solution is optionally heated, and the polymer product isrecovered by flashing off gaseous monomers as well as residual solventor diluent at reduced pressure, and, if necessary, conducting furtherdevolatilization in equipment such as a devolatilizing extruder. In acontinuous process, the mean residence time of the catalyst and polymerin the reactor generally is from 5 minutes to 8 hours, and preferably isfrom 10 minutes to 6 hours.

Alternatively, the foregoing polymerization may be carried out in acontinuous loop reactor with or without a monomer, comonomer, catalystor cocatalyst gradient established between differing regions thereof,optionally accompanied by separate addition of catalysts and/or chaintransfer agent, and operating under adiabatic or non-adiabatic solutionpolymerization conditions or combinations of the foregoing reactorconditions. Examples of suitable loop reactors and a variety of suitableoperating conditions for use therewith are found in U.S. Pat. Nos.5,977,251, 6,319,989 and 6,683,149.

Specific Embodiments

The following embodiments are provided for purposes of specificdisclosure for the appended claims.

1. A process for polymerization of ethylene and one or more C₃₋₃₀α-olefins or diolefins under continuous, solution polymerizationconditions to prepare a high molecular weight interpolymer having narrowmolecular weight distribution and improved processability, said processcomprising conducting the polymerization in the presence of a catalystcomposition comprising a zirconium complex of a polyvalent aryloxyethercorresponding to the formula:

where:

R²⁰ independently each occurrence is a arylene- or inertly substitutedarylene-group of from 6 to 20 atoms not counting hydrogen or any atomsof any substituent, said group being substituted at the positionadjacent to the oxyl-metal bond with a cyclic ligand, said cyclic ligandcontaining from 6 to 30 atoms not counting hydrogen;

T³ is a divalent hydrocarbon or silane group having from 1 to 20 atomsnot counting hydrogen, or an inertly substituted derivative thereof; and

R^(D) independently each occurrence is a monovalent ligand group of from1 to 20 atoms, not counting hydrogen, or two R^(D) groups together are adivalent ligand group of from 1 to 20 atoms, not counting hydrogen.

2. The process of embodiment 1 wherein the resulting polymer has amolecular weight distribution, Mw/Mn, less than 3.0.

3. The process of embodiment 1 wherein the catalyst compositionadditionally comprises a chain transfer agent.

4. The process of embodiment 3 wherein the quantity of chain transferagent present in the reactor is sufficient to decrease the Mw of theresulting polymer at least 30 percent compared to the molecular weightof the resulting polymer prepared in the absence of a chain transferagent.

5. The process of embodiment 3 wherein the chain transfer agent ishydrogen, present in an amount from 0.015 to 2.0 mol percent (based onethylene).

6. The process of embodiment 1 wherein the ethylene conversion is atleast 85 mol percent.

7. The process of any one of embodiments 1-6 wherein a monomer mixtureconsisting essentially of ethylene and one or more C₃₋₂₀ α-olefins ispolymerized.

8. The process of embodiment 7 wherein a monomer mixture consistingessentially of ethylene and one or more C₆₋₂₀ α-olefins is polymerized.

9. The process of embodiment 1 conducted at a temperature from 120 to250° C. to prepare a polymer having a density between 0.855 and 0.950g/cm³, a melt index, I₂, <2.0, a catalyst efficiency of greater than 0.5g_(polymer)/μg_(metal), and I₁₀/I₂≧10.0.

10. The process of embodiment 9 wherein a chain transfer agent ispresent in a quantity such that the decrease in Mw of the resultingpolymer is >30 percent compared to the Mw of the resulting polymer madein the absence of chain transfer agent.

11. The process of embodiment 10 wherein the chain transfer agent ishydrogen present in the reactor in an amount of from 0.015 to 2 molpercent based on ethylene.

12. The process of any one of embodiments 9-11 wherein a monomer mixtureconsisting essentially of ethylene and one or more C₃₋₂₀ α-olefins ispolymerized.

13. The process of embodiment 12 wherein a monomer mixture consistingessentially of ethylene and one or more C₆₋₂₀ α-olefins is polymerized.

14. The process of embodiment 9 wherein the polymer has I₁₀/I₂ from 13to 80.

15. The process of embodiment 1 conducted at a temperature from 120 to250° C. and a catalyst efficiency of greater than 0.5g_(polymer)/μg_(metal) to prepare a polymer having a density between0.855 and 0.950 g/cm³, a melt index, I₂, <5.0, a dissipation factor at130° C. of less than 1 percent, and I₁₀/I₂≧10.0.

16. The process of embodiment 15 wherein a chain transfer agent ispresent in a quantity such that the decrease in Mw of the resultingpolymer is >30 percent compared to the Mw of the resulting polymer madein the absence of chain transfer agent.

17. The process of embodiment 15 wherein the chain transfer agent ishydrogen present in the reactor in an amount of from 0.015 to 2 molpercent based on ethylene.

18. The process of any one of embodiments 15-17 wherein a monomermixture consisting essentially of ethylene and one or more C₃₋₂₀α-olefins is polymerized.

19. The process of embodiment 18 wherein a monomer mixture consistingessentially of ethylene and one or more C₆₋₂₀ α-olefins is polymerized.

20. The process of embodiment 19 conducted at a temperature from 120 to250° C. and a catalyst efficiency of greater than 0.5g_(polymer)/μg_(metal) to prepare a polymer having a density between0.855 and 0.950 g/cm³, a melt index, I₂, <5.0, a dissipation factor at130° C. of less than 1 percent, and I₁₀/I₂ from 13 to 80.

21. A process according to any one of embodiments 1-6 wherein the metalcomplex corresponds to the formula:

wherein:

Ar² independently each occurrence is phenylene or an alkyl-, aryl-,alkoxy- or amino-substituted phenylene group of from 6 to 20 atoms notcounting hydrogen or any atoms of any substituent, and furthersubstituted at the position adjacent to the oxyl-metal bond with apolycyclic aryl group containing from 6 to 30 atoms not countinghydrogen;

T³ is a divalent hydrocarbon bridging group of from 2 to 20 atoms notcounting hydrogen, preferably a divalent substituted or unsubstitutedC₃₋₆ aliphatic, cycloaliphatic, or bis(alkylene)-substitutedcycloaliphatic group; and

R^(D) independently each occurrence is a monovalent ligand group of from1 to 20 atoms, not counting hydrogen, or two R^(D) groups together are adivalent ligand group of from 1 to 40 atoms, not counting hydrogen.

22. The process of embodiment 21 wherein the metal complex correspondsto of the formula:

where

Ar⁴ independently each occurrence is dibenzo-1H-pyrrole-1-yl, naphthyl,anthracen-5-yl, or 1,2,3,4,6,7,8,9-octahydroanthracen-5-yl;

T⁴ independently each occurrence is a propylene-1,3-diyl group, acyclohexan-1,2-diyl group, a bis(alkylene)cyclohexan-1,2-diyl group, acyclohexen-4,5-diyl group, or an inertly substituted derivative thereof;

R²¹ independently each occurrence is hydrogen, halo, hydrocarbyl,trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino ofup to 50 atoms not counting hydrogen; and

R^(D), independently each occurrence is halo or a hydrocarbyl ortrihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2R^(D) groups together are a divalent hydrocarbylene, hydrocarbadiyl ortrihydrocarbylsilyl group of up to 40 atoms not counting hydrogen.

23. The process of embodiment 21 wherein the metal complex correspondsto the formula:

wherein, R^(D) independently each occurrence is chloro, methyl orbenzyl.

24. The process of embodiment 21 wherein the metal complex is selectedfrom the group consisting of:

-   A)    bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-methyl)phenyl)-2-phenoxy)-cis-1,3-cyclohexanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-1,3-cyclohexanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-1,3-cyclohexanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-1,3-cyclohexanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-1,3-cyclohexanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-1,3-cyclohexanediylzirconium (IV)    dibenzyl-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5-cyclohexenediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5-cyclohexenediylzirconium    (TV) dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5-cyclohexenediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5-cyclohexenediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5-cyclohexenediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5-cyclohexenediylzirconium (IV)    dibenzyl-   B)    bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)-1,3-propanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)-1,3-propanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)-1,3-propanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)-1,3-propanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)-1,3-propanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)-1,3-propanediylzirconium (IV)    dibenzyl-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium (IV)    dibenzyl,-   C)    bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)-1,3-propanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)-1,3-propanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)-1,3-propanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)-1,3-propanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)-1,3-propanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)-1,3-propanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dibenzyl 1,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium (IV)    dibenzyl-   bis((2-oxoyl-3-(1,2,3,4,6,7,9,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium (IV)    dibenzyl-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis    4,5-cyclohexenediylzirconium (IV) dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl))phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium (IV)    dichloride, and-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium (IV)    dibenzyl.

25. A polymerization process for polymerization of ethylene and one ormore C₃₋₈ α-olefins using a zirconium complex and an activatingcocatalyst under continuous, solution polymerization conditions at atemperature from 120 to 250° C., preferably from 130 to 250° C., underhigh ethylene conversion conditions (>85 percent, preferably >90percent) characterized in that the resulting polymer has a densitybetween 0.855 and 0.950 g/cm³, preferably between 0.855 and 0.885 g/cm³,Mw/Mn less than 3.0, a melt index (MI) from 0.1 to 40, and I₁₀/I₂>11.75(MI)^(−0.188), preferably I₁₀/I₂>12.72 (MI)^(−0.168.)

26. A copolymer of ethylene and one or more C₃₋₈ α-olefins having adensity between 0.855 and 0.885 g/cm³, Mw/Mn less than 3.0, a melt index(MI) from 0.1 to 40, and I₁₀/I₂>11.75 (MI)^(−0.188), preferably anI₁₀/I₂>12.72 (MI)^(−0.168.)

It is understood that the present invention is operable in the absenceof any component which has not been specifically disclosed and may becombined with any other suitable reaction or process in a multisteppolymerization system design. The following examples are provided inorder to further illustrate the invention and are not to be construed aslimiting. Unless stated to the contrary, all parts and percentages areexpressed on a weight basis.

Examples 1-10 Preparation of Metal Complex

The synthetic procedures of US-A-2004/0010103 were substantiallyrepeated to prepare metal complexes A1-A10.

Continuous Polymerization Conditions

Continuous solution polymerizations are carried out in a computercontrolled autoclave reactor equipped with an internal stirrer. Purifiedmixed alkanes solvent (Isopar™ E available from ExxonMobil, Inc.),ethylene, 1-octene, and hydrogen are supplied to a 3.8 L reactorequipped with a jacket for temperature control and an internalthermocouple. The solvent feed to the reactor is measured by a mass-flowcontroller. A variable speed diaphragm pump controls the solvent flowrate and pressure to the reactor. At the discharge of the pump, a sidestream is taken to provide flush flows for the catalyst and cocatalystinjection lines and the reactor agitator. These flows are measured bymass flow meters and controlled by control valves or by the manualadjustment of needle valves. The remaining solvent is combined with1-octene, ethylene, and hydrogen and fed to the reactor. A mass flowcontroller is used to deliver hydrogen to the reactor as needed. Thetemperature of the solvent/monomer solution is controlled by use of aheat exchanger before entering the reactor. This stream enters thebottom of the reactor. The cocatalyst used is a long-chain alkylammonium borate of approximate stoichiometry equal tomethyldi(octadecyl)-ammonium tetrakis(pentafluorophenyl)borate (MDB)combined with a tertiary component, tri(isobutyl)aluminum modifiedmethalumoxane (MMAO) containing a molar ratio of i-butyl/methyl groupsof about 1/3. The catalyst component solutions are metered using pumpsand mass flow meters and are combined with the catalyst flush solventand introduced into the bottom of the reactor. The reactor is runliquid-full at 500 psig (3.45 MPa) with vigorous stirring. Product isremoved through exit lines at the top of the reactor. All exit linesfrom the reactor are steam traced and insulated. Polymerization isstopped by the addition of a small amount of water into the exit linealong with any stabilizers or other additives and passing the mixturethrough a static mixer. The product stream is then heated by passingthrough a heat exchanger before devolatilization. The polymer product isrecovered by extrusion using a devolatilizing extruder and water cooledpelletizer.

More process details and results are contained in Tables 1 and 2, whileTable 3 contains polymer data from runs in Table 2.

TABLE 1 Solvent C₂H₄ C₈H₁₆ Poly Metal Flow Flow Flow prod. H₂ ¹ C₂H₄ ² TDensity Mw Mw/ Run Comp. (kg/h) (kg/h) (kg/h) (kg/h) (sccm) Conv. (° C.)Eff.³ MI I₁₀/I₂ (g/cc) (×10³) Mn 1 A1 12.7 1.68 0.91 1.84 52.1 91.6 2001.1 0.91 11.6 0.910 72 1.99 2 A1 11.7 1.25 2.72 1.80 7.2 91.5 180 1.40.97 11.1 0.870 97 2.00 3 A2 13.3 1.68 0.52 1.79 46.5 93.5 190 7.6 0.9413.0 0.911 71 2.02 4 A2 13.3 1.68 0.68 2.03 36.9 91.7 201 2.6 1.00 13.10.908 73 1.99 5 A2 12.7 1.25 1.84 1.84 3.0 91.2 179 2.1 0.42 18.2 0.868109 2.52 6 A2 ″ ″ 1.80 1.81 3.2 91.1 183 1.5 0.86 15.5 0.869 99 2.56 7A2 ″ 1.91 0.11 1.79 109.9 92.5 200 3.2 0.86 14.2 0.934 66 2.02 8 A2 ″1.59 0.91 1.77 74.9 91.6 200 1.4 37.2 8.19 0.904 39 1.83 9 A2 11.0 1.770.68 1.83 53.9 89.6 190 4.3 1.01 12.4 0.910 79 2.21 10 A2 ″ ″ ″ 1.8355.0 89.3 185 7.3 1.09 11.8 0.909 70 2.11 11 A2 ″ ″ ″ 1.85 54.9 89.6 17512.0 1.01 11.9 0.908 70 2.05 12 A2 13.8 2.21 0.85 2.30 71.0 89.6 17511.5 1.08 11.3 0.908 72 1.97 13 A2 ″ ″ ″ 2.34 75.7 89.1 165 14.4 0.9611.6 0.909 71 2.12 14 A2 ″ ″ ″ 2.25 69.9 86.0 185 8.3 1.03 12.1 0.909 752.02 15 A2 ″ ″ 0.99 2.04 86.0 80.0 185 4.6 0.99 10.8 0.910 72 2.03 16 A213.0 1.25 1.91 1.71 11.0 85.3 170 3.9 1.03 13.0 0.871 77 2.08 ¹H₂ flow,standard cm³/min ²mol percent ethylene conversion in reactor³efficiency, g PE/μg Zr

TABLE 2 C₈H₁₆ Poly Borate MMAO Flow produced H₂ ¹ C₂H₄ ² T Run CatalystRatio Ratio (kg/h) (kg/h) (sccm) Conv. (° C.) Eff.³ 17 A7 0.0 50.4 0.61.7 62 90.5 160 4.0 18 A8 0.0 50.3 1.7 74 90.3 160 1.0 19 A9 0.0 49.22.1 47 89.9 160 5.5 20 A4 1.1 4.8 1.8 73 91.4 160 1.2 21 A5 1.1 5.0 0.51.7 38 90.6 160 1.8 22 A6 1.1 5.0 0.6 1.9 41 90.4 160 2.1 23 A2 1.1 4.90.5 2.1 50 92.9 190 6.6 24 A7 0.0 50.2 0.6 2.0 53 91.7 190 2.2 25 A8 0.050.4 1.6 35 89.7 190 0.6 26 A9 0.0 50.4 1.9 25 92.5 190 1.8 27 A4 1.15.0 1.7 35 91.4 190 0.9 28 A5 1.1 4.9 0.5 ″ 30 87.0 190 0.3 29 A6 1.15.0 0.6 1.8 6 88.4 190 0.8 ¹standard cm³/min ²mol percent ethyleneconversion in reactor ³efficiency, g PE/μg Zr Solvent flow for all runsis 12.6 kg/hr, C₂H₄ flow for all runs is 1.7 kg/hr

TABLE 3 Density Run MI I₁₀/I₂ (g/cc) Mw Mw/Mn 17 1.00 12.4 0.909 69,8802.02 18 1.59 9.5 0.911 73,240 2.08 19 1.06 13.6 0.910 65,670 2.32 200.95 13.0 0.917 63,340 2.28 21 1.05 10.2 0.909 73,470 1.98 22 1.09 10.10.908 77,780 1.95 23 0.93 12.7 0.910 67,940 2.12 24 0.98 13.2 0.91067,080 2.32 25 0.86 12.0 0.910 93,540 2.24 26 0.87 14.4 0.911 67,1502.39 27 0.88 13.9 0.917 65,710 2.24 28 1.03 10.8 0.914 83,590 2.01 291.03 11.0 0.909 115,570 2.16

The above results indicate that unique ethylene/1-octene copolymers canbe formed having high I₁₀/I₂ and relatively high comonomer incorporationemploying the present invented process.

1. A process for polymerization of ethylene and one or more C₃₋₃₀α-olefins or diolefins under continuous, solution polymerizationconditions to prepare a high molecular weight interpolymer having narrowmolecular weight distribution and improved processability, said processcomprising conducting the polymerization in the presence of a catalystcomposition comprising a zirconium complex of a polyvalent aryloxyethercorresponding to the formula:

where: R²⁰ independently each occurrence is a arylene- or inertlysubstituted arylene-group of from 6 to 20 atoms not counting hydrogen orany atoms of any substituent, said group being substituted at theposition adjacent to the oxyl-metal bond with a cyclic ligand, saidcyclic ligand containing from 6 to 30 atoms not counting hydrogen; T³ isa divalent hydrocarbon or silane group having from 1 to 20 atoms notcounting hydrogen, or an inertly substituted derivative thereof; andR^(D) independently each occurrence is a monovalent ligand group of from1 to 20 atoms, not counting hydrogen, or two R^(D) groups together are adivalent ligand group of from 1 to 20 atoms, not counting hydrogenwherein a chain transfer agent is present in an amount sufficient todecrease the Mw of the resulting interpolymers at least 10 percentcompared to the molecular weight of the resulting polymer prepared inthe absence of a chain transfer agent, the polymerization is conductedat a temperature from 120° C. to 250° C., the ethylene conversion is atleast 85 mol percent and the resultant polymer has a density between0.855 and 0.950 g/cm³, a molecular weight distribution (Mw/Mn)<3.0; amelt index I₂<5.0 and a melt index ratio I₁₀/I₂≧10.0.
 2. The process ofclaim 1 wherein the quantity of chain transfer agent present in thereactor is sufficient to decrease the Mw of the resulting polymer atleast 30 percent compared to the molecular weight of the resultingpolymer prepared in the absence of a chain transfer agent.
 3. Theprocess of claim 1 wherein the chain transfer agent is hydrogen, presentin an amount from 0.015 to 2.0 mol percent (based on ethylene).
 4. Theprocess of claim 1 wherein a monomer mixture consisting essentially ofethylene and one or more C₃₋₂₀ α-olefins is polymerized.
 5. The processof claim 4 wherein a monomer mixture consisting essentially of ethyleneand one or more C₆₋₂₀ α-olefins is polymerized.
 6. The process of claim1 conducted to prepare a polymer having a density a melt index, I₂,<2.0, and a catalyst efficiency of greater than 0.5g_(polymer)/μg_(metal).
 7. The process of claim 6 wherein the chaintransfer agent is present in a quantity such that the decrease in Mw ofthe resulting polymer is >30 percent compared to the Mw of the resultingpolymer made in the absence of chain transfer agent.
 8. The process ofclaim 7 wherein the chain transfer agent is hydrogen present in thereactor in an amount of from 0.015 to 2 mol percent based on ethylene.9. The process of any one of claims 6-8 wherein a monomer mixtureconsisting essentially of ethylene and one or more C₃₋₂₀ α-olefins ispolymerized.
 10. The process of claim 9 wherein a monomer mixtureconsisting essentially of ethylene and one or more C₆₋₂₀ α-olefins ispolymerized.
 11. The process of claim 6 wherein the polymer has I₁₀/I₂from 13 to
 80. 12. The process of claim 1 conducted at a catalystefficiency of greater than 0.5 g_(polymer)/μg_(metal) to prepare apolymer having a dissipation factor at 130° C. of less than 1 percent.13. The process of claim 12 wherein a chain transfer agent is present ina quantity such that the decrease in Mw of the resulting polymer is >30percent compared to the Mw of the resulting polymer made in the absenceof chain transfer agent.
 14. The process of claim 12 wherein the chaintransfer agent is hydrogen present in the reactor in an amount of from0.015 to 2 mol percent based on ethylene.
 15. The process of any one ofclaims 12-14 wherein a monomer mixture consisting essentially ofethylene and one or more C₃₋₂₀ α-olefins is polymerized.
 16. The processof claim 15 wherein a monomer mixture consisting essentially of ethyleneand one or more C₆₋₂₀ α-olefins is polymerized.
 17. The process of claim16 to prepare a polymer having a I₁₀/I₂ from 13 to
 80. 18. A processaccording to claim 1 wherein the metal complex corresponds to theformula:

wherein: Ar² independently each occurrence is phenylene or an alkyl-,aryl-, alkoxy- or amino-substituted phenylene group of from 6 to 20atoms not counting hydrogen or any atoms of any substituent, and furthersubstituted at the position adjacent to the oxyl-metal bond with apolycyclic aryl group containing from 6 to 30 atoms not countinghydrogen; T³ is a divalent hydrocarbon bridging group of from 2 to 20atoms not counting hydrogen, preferably a divalent substituted orunsubstituted C₃₋₆ aliphatic, cycloaliphatic, orbis(alkylene)-substituted cycloaliphatic group; and R^(D) independentlyeach occurrence is a monovalent ligand group of from 1 to 20 atoms, notcounting hydrogen, or two R^(D) groups together are a divalent ligandgroup of from 1 to 40 atoms, not counting hydrogen.
 19. The process ofclaim 18 wherein the metal complex corresponds to of the formula:

where Ar⁴ independently each occurrence is dibenzo-1H-pyrrole-1-yl,naphthyl, anthracen-5-yl, or 1,2,3,4,6,7,8,9-octahydroanthracen-5-yl; T⁴independently each occurrence is a propylene-1,3-diyl group, acyclohexan-1,2-diyl group, a bis(alkylene)cyclohexan-1,2-diyl group, acyclohexen-4,5-diyl group, or an inertly substituted derivative thereof;R²¹ independently each occurrence is hydrogen, halo, hydrocarbyl,trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino ofup to 50 atoms not counting hydrogen; and R^(D), independently eachoccurrence is halo or a hydrocarbyl or trihydrocarbylsilyl group of upto 20 atoms not counting hydrogen, or 2 R^(D) groups together are adivalent hydrocarbylene, hydrocarbadiyl or trihydrocarbylsilyl group ofup to 40 atoms not counting hydrogen.
 20. The process of claim 18wherein the metal complex corresponds to the formula:

wherein, R^(D) independently each occurrence is chloro, methyl orbenzyl.
 21. The process of claim 18 wherein the metal complex isselected from the group consisting of: A)bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium(IV) dimethyl,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium(IV) dichloride,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium(IV) dibenzyl,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium(IV) dimethyl,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium(IV) dichloride,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium(IV) dibenzyl,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium(IV) dimethyl,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium(IV) dichloride,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium(IV) dibenzyl,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium(IV) dimethyl,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium(IV) dichloride,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium(IV) dibenzyl,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-1,3-cyclohexanediylzirconium(IV) dimethyl,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-1,3-cyclohexanediylzirconium(IV) dichloride,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-1,3-cyclohexanediylzirconium(IV) dibenzyl,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-1,3-cyclohexanediylzirconium(IV) dimethyl,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-1,3-cyclohexanediylzirconium(IV) dichloride,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-1,3-cyclohexanediylzirconium(IV) dibenzylbis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5-cyclohexenediylzirconium(IV) dimethyl,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5-cyclohexenediylzirconium(IV) dichloride,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5-cyclohexenediylzirconium(IV) dibenzyl,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5-cyclohexenediylzirconium(IV) dimethyl,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5-cyclohexenediylzirconium(IV) dichloride,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5-cyclohexenediylzirconium (IV) dibenzyl B)bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)-1,3-propanediylzirconium(IV) dimethyl,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)-1,3-propanediylzirconium(IV) dichloride,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)-1,3-propanediylzirconium(IV) dibenzyl,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)-1,3-propanediylzirconium(IV) dimethyl,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)-1,3-propanediylzirconium(IV) dichloride,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)-1,3-propanediylzirconium(IV) dibenzylbis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium(IV) dimethyl,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium(IV) dichloride,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium(IV) dibenzyl,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium(IV) dimethyl,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium(IV) dichloride,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium(IV) dibenzyl,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium(IV) dimethyl,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium(IV) dichloride,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium(IV) dibenzyl,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium(IV) dimethyl,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium(IV) dichloride,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium(IV) dibenzyl,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium(IV) dimethyl,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium(IV) dichloride,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium(IV) dibenzyl,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium(IV) dimethyl,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium(IV) dichloride,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium(IV) dibenzyl, C)bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)-1,3-propanediylzirconium(IV) dimethyl,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)-1,3-propanediylzirconium(IV) dichloride,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)-1,3-propanediylzirconium(IV) dibenzyl,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)-1,3-propanediylzirconium(IV) dimethyl,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)-1,3-propanediylzirconium(IV) dichloride,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)-1,3-propanediylzirconium(IV) dibenzyl,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium(IV) dimethyl,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium(IV) dichloride,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium(IV) dibenzyl,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium(IV) dimethyl,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium(IV) dichloride,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans-1,2-cyclohexanediylzirconium(IV) dibenzylbis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium(IV) dimethyl,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium(IV) dichloride,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium(IV) dibenzylbis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium(IV) dimethyl,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium(IV) dichloride,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-1,3-cyclohexanediylzirconium(IV) dibenzyl,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium(IV) dimethyl,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium(IV) dichloride,bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium(IV) dibenzyl,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium(IV) dimethyl,bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium(IV) dichloride, andbis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5-cyclohexenediylzirconium(IV) dibenzyl.
 22. The process of claim 1 wherein the resulting polymerhas I₁₀/I₂>11.75 (MI)^(−0.188).